Nucleophilic Substitution part 1

What is a nucleophile?

a nucleophile is an electron rich species that can donate a pair of electrons

A nucleophile has either a full negative charge such as CN- or a lone pair as in water or ammonia.

The main nucleophiles for AS are: CN-, OH-, H2O, NH3 (or any other amine e.g. CH3NH2).

For the negatively charged nucleophiles, the reagent (the thing you start with) for CN- is usually KCN
and for OH-, something like NaOH. With H2O and NH3, both are the nucleophile and the reagent.

Halogenoalkanes

the main reaction of halogenoalkanes is nucleophilic substitution

A halogenoalkane has a polar carbon-halogen bond as shown below due to differences in

electronegativity. The carbon atom with the + is open to attack by nucleophiles.

Nucleophilic Substitution Mechanism

The reaction mechanism for nucleophilic substitution is much easier than for electrophilic addition. Its
just one easy step:

The lone pair on the CN- is attracted to the positive charge on the carbon atom (remember negative goes
towards positive).

A second arrow is then required to remove the Br as Br- by breaking the C-Br bond.

Just remember that the halogen atoms like to leave as the halide ion.
 Beware that when using CN-, it is a carbon nucleophile and a new carbon-carbon bond is formed.
Sometimes students get confused as the minus sign appears to be on the nitrogen but its just
written that way for convenience.

If you did the same reaction with water or ammonia, then an extra arrow is involved.

As we are starting with a neutral molecule, we need to put a positive charge on the N or O to show that
we have used the lone pair.

We have to then lose a hydrogen atom attached to the N to neutralise the charge. Usually another NH3
molecule will swoop in to do this:

A lot of students get this part wrong. If an atom has a + charge on it, then we cant leave it like that.
To remove this charge, it has to gain electrons, as it is currently lacking electrons. So the only way is
for something else to give it a pair of electrons. Therefore the arrow must go towards the + charge.

Further Substitution
After adding NH3, as in the example above, an amine is formed which still has a lone pair of electrons.
This means that the amine formed can react again with another halogenoalkane. This can continue until
the N has no lone pairs left.

The final product is a quaternary ammonium salt where the N has a + charge on it.

Rate of hydrolysis
Hydrolysis: the breaking of a bond by the addition of a small molecule. In the example above, the
breaking of the C-Br bond is an example hydrolysis.

This type of bond breaking is known as heterolytic fission i.e. two different fragments are produced.

A favourite question is to change the halogen and to ask which bond would break the fastest or which
reaction has the fastest rate or which has the fastest rate of hydrolysis (they all mean the same thing).

The order from fastest to slowest:

C-I > C-Br > C-Cl > C-F

This is simply because the C-I bond is weakest and is therefore the easiest to break. They might give you a
table with the bond enthalpies but you are just talking about the same things. It shows that the C-I bond
is weakest and therefore breaks first, therefore the reaction is fastest.

C-I C-Br C-Cl C-F

Bond enthalpy (kJ mol-1 ) +238 +276 +338 +484

The bond strength is just down to the size of the halogen. Iodine is biggest and therefore the electrons in
the bon are further from the nucleus less attraction.

Polarity

The other factor that affects the reactivity is the polarity of the carbon-halogen bond. As C-F is the most
polar, the carbon will have a strong + charge and will attract the nucleophile more than the other
halogens would, which should increase the rate of hydrolysis. This contradicts our theory above.

But, the bond strength is the more important factor when explaining why C-I is hydrolysed fastest. I
wouldnt talk about polarity here unless they ask about it.

Monitoring the reaction

There have been several questions on experiments to do with the rate of hydrolysis of halogenoalkanes.

It is quite simple. To monitor the rate of hydrolysis you have to measure something. This is done in two
steps:

1. The halide ion must firstly be substituted from the halogenoalkane to get the halide ion free in
solution. This is just a normal nucleophilic substitution reaction by adding water.

2. Add AgNO3 to react with the displaced halide ion. This is now the usual halide ion test as done in
the Group 7 topic. AgNO3 reacts with the halide ion to give precipitates: AgCl (white), AgBr
(cream) and AgI (yellow). You are looking to time how long it takes for the precipitates to form
and therefore which forms quickest is the fastest rate i.e. from the iodide.